Studies on Zn(II) and Cd(II) heteroligand complexes with RC(S)NHP(O)(OiPr)2 (R = Ph, NH2, PhNH) and α-diimine (bpy and phen) ligands. C-Cl bond cleavage of CH2Cl2 by [Zn(phen){PhC(S)NP(O)(OiPr)2}2]

The reaction of ZnL^I,II₂] (L^I = NH₂C(S)NP(O)(OiPr)₂]⁻; L^II = PhNHC(S)NP(O)(OiPr)₂]⁻) or Cd₂L^IV₄] (L^IV = PhC(S)NP(O)(OiPr)₂]⁻) with 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) leads to the heteroligand complexes Zn(bpy)L^I,II₂], Zn(phen)L^I,II₂], Cd(bpy)L^IV₂] or Cd(phen)L^IV₂], respectively. The introduction of the diimine ligands into the coordination sphere of the metal cation provokes a change from 1,5-O,S- to 1,3-N,S-coordination of the anionic ligands for Zn but not for the Cd species. The reaction of Zn(phen)L^IV₂] (L^IV = PhC(S)NP(O)(OiPr)₂⁻) with CH₂Cl₂ cleaves the chlorine atoms from CH₂Cl₂ and leads to the formation of Zn(phen)L^IVCl] and S,S′-bis(benzimidothio-N-diisopropoxyphosphoryl)methane (L^IV-CH₂-L^IV) in high yields. Using CHCl₃ or CCl₄ instead of CH₂Cl₂ does not lead to the formation of chlorine substituted products even under reflux conditions. The new compounds were investigated by ¹H and ³¹P{¹H} NMR, IR spectroscopy and microanalysis. Crystal structures of ZnL^II₂], Cd(phen)L^IV₂]·CH₂Cl₂, Zn(bpy)L^I₂] and Zn(phen)L^IVCl] were elucidated by X-ray diffraction.